1-arylamino-5-hydroxynaphthalene-7-sulphonic acid



wherein R ?a tenied Apr; 18, 1944 v tiara ir oust i-aitumnoj-anrnnommrnrnnma 7-SULPEONIC new -"Richard Fleischhauerand Adu t.Muller, for;-on-th-Main-Feclieniieim,

Germany; 'assigners to General Aniline & Filin- Corporation,

New Yorlg N. Y., a corporation No Drawing. Application Mal/"20, 1941Serial oi? Delaware -No. 394,284. In Germany May 21, 194i) 4 clai s.fun. ne

, our'present invention relates to l-aryIaminoe-7-sulphonic acids-fol?the fi-hydroxyn phthale general formula:

10 wherein R stands for a radicle of the group consisting of the.benzene and naphthalene series, I

which are new compounds, hitherto unknown in literature. They areobtainable by actingwith primary amines of the general'iormula RNH2, hasthe aforesaid signification in the presence of salts thereof on the1-amino-5-hydroxynaphthalene-bsulphonic acid. at tempera-- tures above130 preferably ranging from..150 to 170, advantageously ,in ;a closed'vessel in the' presence of water. The addition of benzoic acid may be afurther advantage. In this manner. the

tainable with a good yield'and without the formation of amountsof-decomposition products that are worth mentioning. This fact is verynew compounds are obsurprising; since the 1-amino5-hydroxynaphthalene-7-sulphonic acid as-s'uch is easily oxidiza b1e'and the same process isapplicableon isO-- materials-only at meric andanalogous startin lower temperatures, whereas at temperatures above 130"large quantities'oflundesired products of decomposition are formed.

v The present process may be varied by startin from the.1-naphthylamine-5.7 disu1phonic acidand reacting thereupon withtlieprimary amines,

advantageously in the presence of salts thereof. The hitherto unknown 1-arylaminonaphthalene- 5.7-disu1phonic acids, formed thereby with a goodyield, are then transiormed into the l-arylaminonaphthalene-5-hydroxy7-sulphonic acids by the'fusion with caustic alkalies.

Another method of producingthe present reaction products' consists inacting. at higher temperatures preferably ranging from to 150 with theprimary aminocompoundsin the pres-.- ence of salts of sulphurous acid on1-amin'o-5- hydroxynaphthalene-7-sulphonic acid, or1.5-dihydroxy-naphthalene-7-sulphonic acid or salts thereof. This methodallows starting from eas- "ily 'oxidizable amino-compounds such asaromatic diamlnoor --'aminohydroxycompmmds moreover from aminocompounds,containing a solubilizing 7 group suchas a carboxylicor-sulphonic acidarylamino-5-hydroxy naphtha1ene-7 sulphonic acids are when dry colorlessto slightly reddish to greenish gray powders, easily soluble in alkalinesolutions and mostly soluble in hot water.

Their alkali metal salts are easily soluble in water and can be isolatedtherefrom in most cases by adding salt thereto. They are valuableintermediates for the production of dyestufis, particularly ofazodyestuffs. In order to further illustrate our invention the followingexamples are given, the parts being by weightan'd'all' temperatures indegrees centigrade.

v Example i A mixture of 239 parts ofj 1=amino-5-hydroxy naphthalene'l-sulphonic acid,- 500 parts of aniline, parts of hydrochloric acid of-1.l60'density and aboutffioo parts of. water is heated in a.

closed vessel'for 12 to 15 hours at to 160". After the addition of 60parts of sodium hydroxthe remaining liquor, which has been filtered, thesodium-salt of l-phenylamino-d-hydrqsynaphthalene-'T-sulphonlc acid ofthe formula;

Hogs

separates after the addition of salt. 11; crystal: .iiz'es as smallnearly colorless needles. The yield is good. l When heating a mixture of239 parts of l-arnino-fi-hydroxynaphthalenefl-sulphonic acid, 400 partsof aniline and 140 parts of aniline hydrochloride in; an open vesselprovided with a refrigerator while stirrin'gat150 to the same 1phenylamino -5 hydroxynaphthalene -7 -sul- 5 phonic acid is obtained ina gocd yield.

roup. An-alternativemethod consists in decom posing the ,sulphurous acidester of 1.'5-dihy-" droxy-naphthalene-7-sulphonic acid by means'of theaforesaid primary Iamines; The present 1- ide the aniline is distilledOE With steam. From.

When heating in an autoclave as described above a mixture ofl-amino-S-hydroxynaphthalene-7-sulphonic acid hydrochloric acid, Waterand the equivalent amount of 4-methoxy-1- as nobenzene 1 (4'methoxyphenylamino) -5-hydroxynaphthalene 7-sulphonic acid of theformula:

HOaS

s obtained in a very good yield. Its sodium salt :rystallizes asslightly greenish leaflets.

When acting in the same manner with 4- nethyl-l-aminobenzene there isobtained an :xcellent yield of 1-(4'-methylphenyl)aminoi-hydroxynaphthalene-7-su1phonic acid of the i'ormula:

which is advantageously isolated in the form of ;he free acid, thesodium salt being too easily ixidizable.

Example 2 [t is isolated as described in the foregoing ex";

ample.

Example 3 p A mixture of 325 parts of the monsodium salt )fl-aminonaphthalene-5.7-disulphonic acid, 400 parts of aniline and 140parts of aniline hydro- :hloride is heated for about 24 hours at about[$0 to 170. After neutralisation with a caustic soda solution the excessof aniline is removed 0y steam distillation and the remaining liquor ispurified by filtration. By adding sodium chlo-= ride to the solution thedisodium salt of the l-phenylaminonaphthalone-5.7-disulphonic acid isobtained as a slightly yellowish powderin a good yield.

423 parts of this salt are added slowly at 170 :0 175 to a mixture of1500 parts of sodium nydroxide and 200 parts of water. After heating it1'75 to 180 for an hour the reaction mass, he- .ng at th beginningthinly liquid, becomes very viscous. It is then diluted with water andacidiled with hydrochloric acid. The reaction prodict, which separatesin an oily state, becomes :rystalline after standing for a longer timeIt s identical with the l-phenylamino-fi-hydroxyaapthalene-l-sulphonicacid as described in the foregoing examples. d

Example 4 A mixture or 261 parts of the sodium salt of l amino 5hydroxynaphthalene-l-sulphonic acid, 1100 parts of a sodium bisulphitesolution of 1.333 density and 500 parts of 4-methyl-1- aminobenzene isheated in a closed vessel at to for about 48 hours. After the additionof sodiumcarbonate' until a slightly alkaline reaction the excess 01'4-methy1-1-aminobenzene is distilled off and the remaining liquor isacidifled by means of hydrochloric acid and boiled oil in order toremove the sulphurous acid. 1-(.4'- methylphenylamino) 5hydrozwnapthalene- 7-sulphonic acid is obtained in a good yield asnearly colorless crystals cf. the third paragraph of Example 1.

In the same manner by acting with Z-methylaminobenzene,3-methylaminobenzene, 4-methoxy-l-aminoben'zene, 4 phenoxy 1aminobenacne and l-naphthylamine respectively the corresponding 1 (2'methylphenylamino) 5 hydroxynaphthalene 7 sulphonic acid, 1 (3',methylphenyl) amino 5 hydroxynaphthalene- 7-sulphonic acid, 1-(4'-methoxyphenyl) amino-5- hydroxynaphthalene-l-sulphonic acid: (ct.paragraph 4 of Example 1), l-4'-phenoxypheny1)amino-S-hydroxynaphthalene 7 Q sulphonic acid and 1-(1'-naphthyl)-amino-5-hydroxynaphthaiene-Y-sulphonic acid or the formula:

are obtained.

Example 5 A mixture of 261 parts of the sodium salt of l amino 5hydroxynaphthalene '7 sulphonic acid, 1100 parts ofa sodium-blsulphitesolution of 1.333 density and 200 parts 01' 4-hydroxy 1 aminobenz'ene 3carboxylic acid is boiled for a longtime under reflux, until thesulphurous acid ester of the 1.5-dihydroxynaphthalene-l-sulphonic acidformed as intermediate is decomposed. The excess 01'4-hydroxy-1-aminobenzene-3-carboxylic acid is removed after cooling byfiltration. After acidification with hydrochloric acid and removal ofthe sulphurous acid and in a given case the addition of sodium chloridethe 1-(4-hydroxyl-3'-carboxyphenyl)-amino-5-hydroxynaphthalene-'l-sul1phonic a c i d of the formula:

NH-Q-OH benzene-3-carboxylic acid and from 1 (4'-aminobenzoylamino) 4hydrcxybenzene 3 carboxylic acid respectively the1-(3-carboxy-phenylamino) -5-hydroxynaphthalene-7-su1phonic acid of theformula:

OOH

being an almost colorless powder, easily soluble in alkaline solutionsand the 4-(5"-hydroxy-'7"-,- sulpho 1" naphthylamino) benzoyl (4'hydroxy-3-carboxypheny1) amide of the formula:

HOaS- 00 OH are obtainable.

I Example 6 A mixture of 2'71 parts of the sodium salt of 1amino-S-hydroxynaphthalene '7 sulphonic acid, 14 00iparts'oi a sodiumbisulphite solution of 1.333 density and 180parts of4.4'-diaminodiphenyl is heated for about 40 hours in an autoclave at120130 125.

water, strongly acidified with hydrochloric acid phenyl being dissolved,whereas the new condensation product remains undissolved. The isolatedand dried 1-(4'-aminodiphenyl) amino-5-hydr'oxynz'aphthalene-I-sulphonic acid of the formula:

is an almost colorless powder soluble in a dilute sodiumcarbonatesolution.

When replacing the 4.4'-diaminodiphenyl by 4- aminodiphenylamine the 1(4 pheriylaminophenyl) amino 5 hydroxynaphthalene '7 sulphonic acid ofthe-formula:

iG 0 I When cool the condensation product is isolated. It isdiluted withmuch and boiled 0115, the unchanged 4.4'-diamino-diis obtained.

Example 7 261 parts of the sodium 'salt' of 1-amino-5-hydroxynaphthalene-7-sulphonic acid are mixed with 1100 parts of asodium bisulphite solution of 1.000 density and 220 parts of1.4-diaminobenzene and the mixture is boiled for about '24 hours underreflux. When cool the formed precipi tate is separated by filtrationfrom the bisulphite liquor and extracted with a hot dilute hydrochloricacid. The 1-(4'-aminophenyl)amino-5- hydroxynaphthalene-7-sulphonic acidof the formula:

separates in a crystalline form and is when dry a slightly greenishpowder soluble in a dilute sodium carbonate solution.

By treatment with acylating agents such as acetic acid anhydride,benzoylchloride or chloroiormic acid ethylester in the presence of anacid binding agent the 1 (4' acetylaminophenyl)amino-5-hydroxynaphthalene-'7-sulphonic acid, the 1-(4-benzoylaminophenyl) amino-5-hydroxynaphthalene-7-sulpho'nic acid,1-(4'-carbethoxyaminophenyl) amino 5 hydroxynaphtha- 'lene-7-sulphonicacid and similar compounds areformed.

Example 8 n'HOsAm c 0 on HOJS is isolated by adding sodium chloride. Itis when dry a slightly grayish powder easilysoluble in a dilute sodiumcarbonate solution.

When replacing the 1-aminobenzene-4-thioglycollic acid by1-aminobenzene-4-hydroxyacetic acid, 1 aminobenzene 4-aminoethansulphonic acid, 1 aminobenzene-4-aminoacetic acid vor1-amino-4-oxalyl-aminobenzine the corresponding products of theformulae:

NHOO om-c 0 OH I IHONH-CHl-CHP'SOQH Example 9 A mixture of 261 parts ofthe sodium salt of l-amino hydroxynaphthalene '7 sulphonic acid, 1100parts of a sodiumbisulphite solution of 1.333 density and 500 parts of4.4'-diaminodiphenylamino-2-sulphonic acid is boiled for about 24 hoursunder reflux. The formed condensation product of the formula:

HOaS- $03K in is when dry. a slightly grayish powder easilysoluble in adilute sodiumcarbonate solution.

Example 10 239 parts of 1-amino-5-hydroxynaphthalene-'7- sulphonic acidare mixed with 500 parts of water and 40 parts of sodium hydroxide and875 parts of a sodium bisulphite solution of 1.333 density are added.Then the mixture is heated while stirring for about 35 to 40 hours in anautoclave at 125 to 130.

After acidification with hydrochloricacid the sulphurous acid is removedby boiling and, if necessary, a little amount of undecomposed startingmaterial is removed by adding sodium chloride to the aqueous solution.

By evaporisation under a slightl reduced pressure the1.1'-dinaphthylamino-5.5'-dihydroxy- 7.7"sulphonic acid of the formula:

, We claim:

1. l-arylamino 5 hydroxynaphthalene-7-sulphonic acids of the generaltormula:

NH-R

Hoas

wherein R stands for aradlcle of the group consisting of phenyl,alkyl-phenyl, alkoxy-phenyl, phenoxy-phenyl, carboxy-phenyl,carboxy-hydroXy-phenyl, hydroxy-carboxy-N-phenyl carbamyl-phenyl,amino-diphenyl, phenylaminophenyl, aminophenyl, acetylaminophenyl,benzoylaminophenyl, carbethoxyaminophenyl, carboxymethylenethiophenyl,carboxymethyleneoxyphenyl, sulphoethyleneaminophenyl,carboxymethyleneaminophenyl, oxalylaminophenyl, andsulphodiamino-phenyl-N-phenyl, which products are when dry colorless toslightly reddish to greenish gray powders, which are easily soluble inalkaline solutions and mostly soluble in hot water. the alkali metalsalts of which .are easily soluble in water and can be isolated fromaqueous solutions in most cases by adding salt thereto.

2. The 1 (4 methoxyphenylamino) 5 hydroxynaphthalene-7-sulphonic acid ofthe formula:

on being a slightly colored powder easily soluble in alkaline solutions,the sodium salt crystallizinga slightly greenish leaflets.

3. The 1 (3' carboxyphenyl) amino-5-hydroxynaphthalene-7-sulphonic acidof the formula:

OH being an almost colorless powder, easily soluble in alkalinesolution.

4. The 1-(4'-aminodiphenyl) -amino-5-hydroxynaphthalene-'l-sulphonicacid of 'the formula:

H being an almost colorless powder soluble in a dilute sodium carbonatesolution.

RICHARD FLEISCHHAUER. ADOLF MULLER.

